EP0532943B1 - Résine de polyester et son utilisation - Google Patents

Résine de polyester et son utilisation Download PDF

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Publication number
EP0532943B1
EP0532943B1 EP19920114522 EP92114522A EP0532943B1 EP 0532943 B1 EP0532943 B1 EP 0532943B1 EP 19920114522 EP19920114522 EP 19920114522 EP 92114522 A EP92114522 A EP 92114522A EP 0532943 B1 EP0532943 B1 EP 0532943B1
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EP
European Patent Office
Prior art keywords
heat shrinkable
shrinkage
film
mole
polyester film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP19920114522
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German (de)
English (en)
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EP0532943A1 (fr
Inventor
Tatsushi c/o Toyohashi Plants Fukuzumi
Noriyuki c/o Toyohashi Plants Tajiri
Miki Murata
Yasunori c/o Toyohashi Plants Terashima
Tomohiko c/o Toyohashi Plants Yoshida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP490792A external-priority patent/JPH05186579A/ja
Priority claimed from JP5290492A external-priority patent/JPH0565338A/ja
Priority claimed from JP11096492A external-priority patent/JPH05305664A/ja
Priority claimed from JP11096392A external-priority patent/JPH05305663A/ja
Priority claimed from JP11096592A external-priority patent/JPH05261816A/ja
Priority claimed from JP4114890A external-priority patent/JPH068322A/ja
Priority to EP96110824A priority Critical patent/EP0741161A3/fr
Priority to EP96110825A priority patent/EP0741166A3/fr
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Publication of EP0532943A1 publication Critical patent/EP0532943A1/fr
Publication of EP0532943B1 publication Critical patent/EP0532943B1/fr
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a polyester resin for use as a molding material for various moldings such as extrusion molding, blow molding, vacuum molding and injection molding, and particularly to a polyester resin suitable for use as a heat shrinkable polyester film for various packaging materials etc. and a bottle for direct blow molding. More particularly, the present invention is concerned with a polyester resin that can be used as a molding material, such as a bottle for direct blow molding, capable of improving crystallinity and, at the same time, moldability and oxidation stability without detriment to mechanical properties of polyethylene terephthalate and can also be used as a highly shrinkable polyester film having high shrinkage in a relatively low temperature region and excellent heat shrinking properties, such as less liability to uneven shrinkage.
  • a heat shrinkable plastic film has been used for display, protection, binding, improvement in the added value of goods, etc. in the fields of containers, fishing rods, capacitors, rod-shaped fluorescent lamps, etc. and also for multipack and contact packaging for books, notebooks, etc.
  • the development of various applications utilizing the shrinkability and shrinkage stress of the heat shrinkable film is anticipated in many fields other than those described above.
  • Resins such as polyvinyl chloride, polystyrene and polyolefin have hitherto been used as a material for a heat shrinkable plastic film. These resins, however, have had problems with heat resistance, weather resistance, chemical resistance, etc.
  • a polyvinyl chloride film is a heat shrinkable film having various shrinking properties. This film, however, is liable to experience the frequent occurrence of fish eye, and goods, wherein the above film subjected to printing is used as a packing material, have a spoiled appearance and a lower value. In order to obtain a heat shrinkable film free from fish eye, it is necessary to conduct excessive quality control, so problems occur such as a significant increase in the production cost of a film.
  • the polyvinyl chloride is disadvantageous also in that incineration at the time of disposal results in a pollution problem, additives such as a plasticizer in polyvinyl chloride bleed out with the elapse of time to cause staining due to deposition of dust etc. and they are unsafe.
  • the solvent resistance is so low that a special ink should be used for printing.
  • spontaneous shrinkage occurs even at room temperature, the film should be stored in a cold place. Further, it also had a problem with disposal. Specifically, since incineration at a high temperature is necessary, large amounts of black smoke and an offensive smell are unfavorably generated at the time of the incineration.
  • a polyester film is greatly expected as a material capable of solving the above-described problems, and the amount of use thereof has increased.
  • the conventional heat shrinkable polyester film use was made of a copolymer polyester resin comprising a dicarboxylic acid moiety composed mainly of terephthalic acid and a diol moiety composed mainly of ethylene glycol and, copolymerized with the dicarboxylic acid moiety, isophthalic acid, sebacic acid, adipic acid or neopentyl glycol.
  • the conventional heat shrinkable polyester film however, had no satisfactory heat shrinking properties. In particular, uneven shrinkage is liable to occur during shrinkage. For this reason, when the film covers a container, such as a bottle, and is then shrunk, there occurs a problem in that letters or patterns printed on the film are distorted and the adhesion of the film to the container is unsatisfactory.
  • the polyester film is inferior regarding shrinkability at a low temperature and therefore should be shrunk at a high temperature in order to attain the necessary degree of shrinkage, which gives rise to such problems as deformation and bottle whitening etc.
  • the polyester film is used as a label for a polyethylene bottle, since the polyethylene bottle, as such, is inferior to a PET bottle etc. in heat resistance, the shrinking operation should be conducted at the relatively low temperature of about 70°C. For this reason, the development of a heat shrinkable film having excellent shrinking properties at a low temperature has been desired in the art.
  • a heat shrinkable film comprising a copolymer polyester
  • an ethylene oxide adduct of a bisphenol compound or an ethylene oxide adduct of a bisphenol derivative is used as a comonomer component and the retention time of residual stress at the time of the heat treatment is prolonged so as to improve the shrinking properties.
  • Polyethylene terephthalate, polybutylene terephthalate, etc. have generally been used as a polyester resin for a molding material used in direct blow molding or the like. Further, modified polyester resins comprising said resins copolymerized with various monomers, such as isophthalic acid or cyclohexanedimethanol, polyethylene naphthalate comprising an acid moiety composed mainly of naphthalenedicarboxylic acid, etc. have been developed.
  • the mechanical strength properties such as impact strength
  • the melt viscosity of the resin is so low that it is very difficult to conduct molding, a comparison cannot be formed, and in particular, a large container cannot be molded.
  • the modified polyester resin copolymerized with cyclohexanedimethanol is unsatisfactory although an improvement in moldability can be attained over that of a resin copolymerized with isophthalic acid.
  • the heat stability of the resin is so poor that when the resin stays within a molding machine for a long period of time, the deterioration of the resin is significant.
  • Polyethylene naphthalate has the feature that it has a higher melting point than the conventional polyester resins, but, it is unsatisfactory as a resin for a molding material with respect to mechanical properties and moldability.
  • diethylene glycol produced as a by-product is contained in the resin, which leads to a lowering in the moldability and oxidation stability of the resin.
  • An attempt to reduce the diethylene glycol content has been made by the addition of sodium hydroxide or the like during polymerization. Even a polyester resin produced by this method is unsatisfactory with respect to the moldability or oxidation stability although it is possible to reduce the diethylene glycol content to about 1.5% by weight.
  • the present invention provides first a polyester resin comprising units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound; the content of the ethylene oxide adduct of a bisphenol compound being 0-5 to 30% by mole based on the whole diol component, and said resin further comprising 0.1 to 20% by weight of units of polyoxytetramethylene glycol and/or polyethylene glycol.
  • the polyester resin of the present invention comprises units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound.
  • Examples of the aromatic dicarboxylic acid as a main component of the dicarboxylic acid component constituting the polyester resins according to the invention include terephthalic acid, isophthalic acid and naphthalene-1,4- and naphthalene-2,6-dicarboxylic acids.
  • the content of these aromatic dicarboxylic acids in the dicarboxylic acid component is preferably 80% by mole or more, still preferably 85% by mole or more, and when the content of the aromatic dicarboxylic acid is less than 80% by mole, there is a tendency, when it is formed into, for example, a film, to lower the mechanical strength of the polyester film.
  • the dicarboxylic acid component preferably includes terephthalic acid and isophthalic acid.
  • the content of the isophthalic acid based on the whole dicarboxylic acid component is in the range of from 7 to 30% by mole, preferably in the range of from 10 to 30% by mole, still preferably in the range of from 12 to 30% by mole, because when the polyester resin is used as a heat shrinkable label for a container such as a bottle, the heat shrinkable film is used after the ends of the film are solvent-bonded to each other with a solvent, such as tetrahydrofuran, so as render the film in tubular form. Therefore, when the ends are not sufficiently bonded to each other, the label is unfavorably peeled off.
  • the content of isophthalic acid was limited to the above-described range for the purpose of imparting a sufficient solvent-bonding property to the film, and when the content is less than 7% by mole, no sufficient improvement in the solvent-bonding property can be attained. On the other hand, when the content exceeds 30% by mole, shrinking properties, such as uneven and high percentage shrinkage become poor.
  • aliphatic dicarboxylic acids or their ester forming derivatives other than those described above may be incorporated in an amount of less than 20% by mole, preferably less than 15% by mole for the purpose of enhancing the effect of the present invention.
  • these aliphatic dicarboxylic acids are incorporated in an amount of 20% by mole or more, there is a possibility that when the polyester resin is formed into a film, the mechanical properties of the film are lowered.
  • Examples of the aliphatic dicarboxylic acid useable in the present invention include glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid and succinic acid, and when the polyester resin is used as a heat shrinkable film, the incorporation of these aliphatic dicarboxylic acids in a suitable amount contributes to the enhancement of the percentage heat shrinkage.
  • the diol component constituting the polyester resin according to the invention is composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative, and the content of the ethylene oxide adduct of the bisphenol compound or its derivative should be in the range of from 0.5 to 30% by mole based on the whole diol component, because when the polyester resin is used as a heat shrinkable film, if the content of the ethylene oxide adduct of bisphenol A is less than 0.5% by mole, no effect of reducing the uneven shrinkage can be attained, while if the content exceeds 30% by mole, shrinkage at a low temperature is lowered.
  • Examples of the ethylene oxide adduct of the bisphenol compound or its derivative include those having structures represented by the following general formulae (1) and (2). wherein X stands for CH 2 , C(CH 3 ) 2 , C(CF 3 ) 2 , O, S or SO 2 and n and m are each a number satisfying a requirement represented by the formula 2 ⁇ n + m ⁇ 6.
  • X stands for CH 2 , C(CH 3 ) 2 , C(CF 3 ) 2 , O, S or SO 2
  • R stands for a C 1 -C 5 alkyl group or a halogen group
  • n and m are each a number satisfying a requirement represented by the formula 2 ⁇ n + m ⁇ 6 and a and b are each an integer of 1 to 4.
  • an ethylene oxide adduct of bisphenol A having a structure represented by the following general formula (3) is preferred. wherein n and m are each a number satisfying a requirement represented by the formula 2 ⁇ n + m ⁇ 6.
  • the polyester resin contains, as the diol component units, units of polyoxytetramethylene glycol and/or polyethylene glycol together with ethylene glycol and the ethylene oxide adduct of a bisphenol compound or its derivative.
  • the incorporation of polyoxytetramethylene glycol or polyethylene glycol gives rise to the reduction in uneven shrinkage when the polyester resin is used as a heat shrinkable film.
  • the content of the polyoxytetramethylene glycol or polyethylene glycol units in the resin is in the range of from 0.1 to 20% by weight, and preferably in the range of from 0.3 to 15% by weight, because when the polyester resin is used as a heat shrinkable film, if the content of the polyoxytetramethylene glycol or polyethylene glycol is less than 0.1% by weight, the effect of reducing uneven shrinkage is small, while when the content exceeds 20% by weight, the melting point or glass transition point of the resin becomes so low that the film forming properties are lowered.
  • the molecular weight of the polyoxytetramethylene glycol used is preferably in the range of from 300 to 4000, and the molecular weight of the polyethylene glycol is preferably in the range of from 300 to 20000, and when the molecular weight is less than the above-described range, no reduction the uneven shrinkage is attained, while when the molecular weight exceeds the above-described range, compatibility with the resin unfavorably becomes poor.
  • propylene glycol triethylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, etc. may also be used as the diol component in such an amount as will not be detrimental to the effect of the present invention.
  • the heat shrinkable polyester film of the present invention preferably contains units of a tricarboxylic or higher polycarboxylic acid, a trihydric or higher polyhydric alcohol or both.
  • the content of these polycarboxylic acid and/or polyhydric alcohol units is preferably in the range of from 0.01 to 1% by weight, and still preferably in the range of from 0.05 to 0.7% by weight, because when the polyester resin is used as a heat shrinkable film, if the content of the tricarboxylic or higher polycarboxylic acid and/or trihydric or higher polyhydric alcohol units is less than 0.01% by weight, the effect of reducing uneven shrinkage is small, while if the content exceeds 1% by weight, gelation occurs during polymerization to form a polyester.
  • Examples of the polycarboxylic acid used in the present invention include trimellitic acid and pyromellitic acid and their anhydrides.
  • Examples of the polyhydric alcohol include trimethylolpropane, glycerin and pentaerythritol. Among them, trimellitic acid, trimethylolpropane and pentaerythritol are particularly preferred from the viewpoint of film forming properties, heat stability, etc.
  • the above-described polyester resins according to the invention are produced by a known polymerization method such as transesterification or direct polymerization.
  • the resin of the present invention can be produced by charging a reaction vessel with an ester forming derivative of a dicarboxylic acid, such as terephthalic acid, an ethylene oxide adduct of a bisphenol compound or its derivative such as dialkyl esters or diaryl esters and ethylene glycol so that the amount of the whole diol component is 1.8 to 2.5 times, by mole, that of the whole acid component, allowing a transesterification reaction to sufficiently proceed at 150 to 250°C in the presence of a transesterification catalyst, adding a stabilizer, a polymerization catalyst, etc. to the reaction system, heating the system to 260 to 300°C under a reduced pressure of 5 mmHg or less and allowing a reaction to proceed for 3 to 5 hr.
  • the resin of the present invention can be produced by charging a reaction vessel with terephthalic acid, an ethylene oxide adduct of bisphenol A and ethylene glycol so that the amount of the whole diol component is 1.2 to 1.8 times, by mole, that of the whole acid component, heating the mixture to 150 to 260°C with the system being pressurized by nitrogen to allow the esterification to sufficiently proceed, heating the system to 260 to 300°C under a reduced pressure of 5 mmHg or less and allowing a reaction to proceed for 3 to 5 hr.
  • transesterification catalyst used in the production of the polyester resin according to the present invention examples include zinc acetate, manganese acetate, magnesium acetate and titanium tetrabutoxide.
  • polymerization catalyst examples include antimony trioxide, titanium tetrabutoxide, dibutyltin oxide and germanium dioxide, and are added in amounts of 50 to 1000 ppm based on the acid component.
  • the polyester resin of the present invention can be used as a material for various moldings such as extrusion molding, blow molding, vacuum molding and injection molding and are suitable particularly for use as a heat shrinkable polyester film and a polyester bottle for direct blow molding.
  • the treatment include irradiation with ultraviolet rays, ⁇ rays, ⁇ rays, ⁇ rays or an electron beam, treatments such as a corona treatment, a plasma irradiation treatment and a flame treatment, coating of a resin such as vinylidene chloride, polyvinyl alcohol, polyamide or a polyolefin, a laminate and vapor deposition of a metal.
  • the additive examples include resins such as polyamides, polyolefins, polymethyl methacrylate and polycarbonate, inorganic particles such as silica, talc, kaolin and calcium carbonate, pigments such as titanium oxide and carbon black, dyes, ultraviolet absorbers, release agents, flame retardants, antioxidants and heat stabilizers.
  • polyester resin of the present invention as a heat shrinkable polyester film
  • a raw film is formed from the polyester resin of the present invention, preferably the polyester resin according to the invention by a known film forming method, such as a casting roller method or a calender method.
  • the raw film is then stretched 1.5 to 5.0 times the original length in the longitudinal direction or the lateral direction, preferably 1.5 to 4.8 times the original length at a temperature of at least 3°C and preferably at least 5°C above the glass transition temperature of the polyester resin to impart a high percentage shrinkage to the film.
  • the film is further stretched in a direction normal to the above stretching direction 1.0 to 1.8 times, preferably 1.0 to 1.5 times the original length, which is useful for preventing the film from unnecessarily and excessively shrinking in the above stretching direction through enhancement of the tensile strength of the film.
  • the drawing of the film is conducted by simultaneous biaxial stretching, successive biaxial stretching, uniaxial stretching, etc.
  • the stretched heat shrinkable polyester film can be used as a product. Alternatively, it may be heat-treated at a temperature of 50 to 150°C for several seconds to several tens of seconds to attain dimensional stability.
  • the heat treatment can lead to the development of favorable properties such as the adjustment of percentage shrinkage of the polyester film in the direction of shrinkage, reduction in the shrinkage with the elapse of time during storage of an unshrunk film or reduction in the occurrence of a shrink spot, and although the film thickness is not particularly limited, it is usually in the range of from 1 to 600 ⁇ m from a practical viewpoint.
  • packaging applications particularly, in packaging foods, beverages, medicines, etc., use is made of a film having a thickness in the range of from 6 to 380 ⁇ m.
  • the percentage shrinkage of the heat shrinkable polyester film of the present invention prepared by the above method is preferably 20% or more at 60°C in a unidirection (in the direction of shrinkage) when the film is heated in a hot bath for 60 sec.
  • the percentage shrinkage at 60°C is less than 20%, adhesion to a container is unsatisfactory, so that it becomes necessary to increase the heating temperature during the shrinking step.
  • An increase in the heating temperature in the shrinking step gives rise to deformation or a whitening of the container, such as a bottle, and the rapid shrinkage of a heat shrinkable film, which is causative of the occurrence of uneven shrinkage.
  • Shrinkage at 60°C is preferably 25% or more, and still preferably 30% or more.
  • the shrinking initiation temperature of the heat shrinkable polyester film should be 50°C or below for attaining excellent shrinking properties, because when the heat shrinkable polyester film exhibits a percentage shrinkage of 20% or more at 60°C and a shrinking initiation temperature exceeding 50°C, rapid shrinkage occurs at the time of film shrinkage, which leads to uneven shrinkage.
  • the shrinkage at 50°C is preferably at least 1%, and still preferably 2% or more.
  • the average shrinking rate be in the range of from 0.3 to 3 %/sec in a period of each 10 sec between 0 sec and 10 sec, between 10 sec and 20 sec and between 20 sec and 30 sec after immersion.
  • the heat shrinkable polyester film exhibits shrinkage properties such that, when it is immersed in a hot bath, moderate shrinkage behavior occurs and shrinkage occurs evenly 30 sec after immersion, because when the average shrinkage rate of the film in hot water is less than 0.3 %/sec, and since sufficient shrinkage does not occur, the adhesion of the film to a container is unsatisfactory, so that it is necessary to increase the heating temperature during the shrinking step.
  • the average shrinkage rate in hot water is in the range of 0.3 to 3 %/sec in a period of each 10 sec between 0 sec and 10 sec, between 10 sec and 20 sec and between 20 sec and 30 sec after immersion, and the relationship between the immersion time (sec) and the shrinkage (%) is such that the shrinkage increases at a relatively constant rate with the elapse of immersion time and the percentage of increase is relatively moderate. This indicates that when shrinkage for 30 sec after immersion is even, it becomes possible to prevent uneven shrinkage attributable to rapid shrinkage and when moderate shrinkage is maintained for a relatively long period of time, no uneven shrinkage occurs, so that adhesion of the film to a container or the like becomes satisfactory.
  • the percentage of shrinkage was determined by providing marked lines at intervals of 100 mm on a polyester film cut out into 150 mm segments in the direction of stretching and 20 mm in a direction normal to the direction of stretching, heating the polyester film in air at 80°C and 100°C (Examples 1 to 9 and Comparative Examples 1 to 8) or hot water at 50 to 90°C (Examples 10 to 19 and Comparative Examples 9 to 15) without a load for 60 sec, measuring the length before shrinkage (L) and the length after shrinkage (L') in the direction of film shrinkage and determining the percentage shrinkage according to the following equation.
  • Shrinkage (%) ⁇ (L - L')/L ⁇ ⁇ 100
  • a polyester film cut so as to be 150 mm in the direction of stretching and 20 mm in a direction normal to the direction of stretching was heat-shrunk in water at 90°C without application of a load for 60 sec, and the occurrence of uneven shrinkage of the film was evaluated according to the following criteria.
  • the solvent-bondability was evaluated by putting both ends of the polyester film on top of the other, bonding the ends to each other by using tetrahydrofuran as an organic solvent, allowing the polyester film to stand for 24 hr, pulling the bonded surface by hand and evaluating the bonding strength according to the following criteria.
  • the intrinsic viscosity was measured at 25°C by means of a Ubbelohde viscometer in the form of a solution of the polyester resin dissolved in a mixed solvent comprising phenol and 1,1,2,2-tetrachloroethane in a weight ratio of 1 : 1.
  • the glass transition temperature (Tg), melting point (Tm), crystallization peak temperature from a glassy state (Tc + ) and crystallization exothermic peak temperature (Tc - ) from a molten state were determined after raising the temperature of a melt-quenched sample in a nitrogen stream at 280°C at a temperature rise rate of 5°C/min to 280°C in a differential scanning calorimeter (DT-40 manufactured by Shimadzu Seisakusho Ltd.).
  • the shoulder value was adopted in the Tg, and the peak value was adopted in the Tm, Tc + and Tc - values.
  • the impact strength was evaluated in a notch state (impact strength 1) and an unnotched state (impact strength 2) on a specimen of No. 1-A prepared according to a method specified in Izod impact strength (JIS K7110).
  • the diethylene glycol content of the resin was measured by decomposing the resin with hydrazine and filtering the decomposition solution and subjecting the filtrate to gas chromatography.
  • the moldability was evaluated by setting the resin temperature to 210°C for a non-crystalline resin and 240°C for a crystalline resin, extruding a parison having a length of 200 mm, subjecting the parison to direct blow molding and evaluating 10 molded articles according to the following criteria.
  • the oxidation stability was evaluated by subjecting a resin having a water content regulated to 100 ppm or less to extrusion at a resin temperature of 250°C by means of a conventional uniaxial extruder provided with no vent, measuring a change in the IV value between before and after the extrusion and evaluating the oxidation stability in terms of the lowering in the IV value according to the following criteria.
  • a reaction vessel was charged with 100 parts by mole of terephthalic acid, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 147 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 35 ⁇ m.
  • the results of measurement of the percentage shrinkage and the results of evaluation of uneven shrinkage of the resultant film are given in Table 1.
  • a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 30 parts by mole of an ethylene oxide adduct of bisphenol A, 148 parts by mole of ethylene glycol and 20% by weight, based on the polymer, of polyethylene glycol (molecular weight: 10000).
  • Zinc acetate was added thereto as a transesterification catalyst in an amount of 350 ppm based on the whole acid component
  • germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
  • trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component
  • polymerization was conducted by transesterification.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 60°C 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 35 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 1.
  • a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 10 parts by mole of an ethylene oxide adduct of bisphenol S, 150 parts by mole of ethylene glycol and 5% by weight, based on the polymer, of polyethylene glycol (molecular weight: 300).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid moiety
  • germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 70°C 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
  • a reaction vessel was charged with 100 parts by mole of terephthalic acid, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 147 parts by mole of ethylene glycol, 0.01% by weight, based on the polymer, of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to provide a heat shrinkable polyester film having a thickness of 35 ⁇ m.
  • the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
  • a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 30 parts by mole of an ethylene oxide adduct of bisphenol A, 148 parts by mole of ethylene glycol, 0.09% by weight, based on the polymer, of trimellitic anhydride and 20% by weight, based on the polymer, of polyethylene glycol (molecular weight: 10000).
  • Zinc acetate was added thereto as a transesterification catalyst in an amount of 350 ppm based on the whole acid component
  • germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
  • trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by transesterification.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to provide a heat shrinkable polyester film having a thickness of 35 ⁇ m.
  • the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
  • a reaction vessel was charged with 100 parts by mole of terephthalic acid and 150 parts by mole of ethylene glycol.
  • Germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
  • a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 140 parts by mole of ethylene glycol and 70% by weight, based on the polymer, of polyethylene glycol (molecular weight: 1000), and polymerization was conducted in the same manner as that of Example 2.
  • the heat resistance of the resultant polyester resin was so poor that no film could be formed.
  • a reaction vessel was charged with 100 parts by mole of terephthalic acid, 100 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
  • trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component
  • polymerization was conducted by direct polymerization.
  • the degree of polymerization became not increased in the course of the polymerization, so that no polyester resin for forming a film could be obtained.
  • a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 20 parts by mole of an ethylene oxide adduct of bisphenol A and 130 parts by mole of ethylene glycol.
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 200 ppm based on the whole acid component
  • germanium dioxide was added thereto as a polymerization catalyst in an amount of 400 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
  • a reaction vessel was charged with 83 parts by mole of terephthalic acid, 17 parts by mole of isophthalic acid, 130 parts by mole of ethylene glycol and 5% by weight, based on the polymer, of polytetraoxymethylene glycol (molecular weight: 2000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 200 ppm based on the whole acid component
  • germanium dioxide was added thereto as a polymerization catalyst in an amount of 400 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
  • a reaction vessel was charged with 100 parts by mole of terephthalic acid, 60 parts by mole of an ethylene oxide adduct of bisphenol A, 140 parts by mole of ethylene glycol, 0.005% by weight, based on the polymer, of trimellitic acid and 0.05% by weight, based on the polymer, of polyethylene glycol (molecular weight: 1000), and polymerization was conducted in the same manner as that of Example 1.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
  • a reaction vessel was charged with 100 parts by mole of terephthalic acid, 50 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol, 10% by weight, based on the polymer, of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
  • trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component
  • polymerization was conducted by direct polymerization.
  • gelation occurred in the course of the polymerization, so that no polyester resin for forming a film could be prepared.
  • a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 42 parts by mole of an ethylene oxide adduct of bisphenol A, 110 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 300 ppm based on the whole acid content
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid content, and polymerization was conducted by direct polymerization.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
  • the heat shrinkable polyester films of Examples 1 to 9 according to the present invention exhibited a heat shrinkage of 30% or more at 80°C and 40% or more at 100°C, and substantially no uneven shrinkage was observed.
  • Table 2 although heat shrinkable polyester films of Comparative Examples 1, 4, 5, 6 and 8 exhibited a large shrinkage, the occurrence of uneven shrinkage was observed, so that these films are not practical.
  • a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Antimony trioxide was added thereto as a polycondensation catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 60 ppm based on the whole acid component
  • germanium dioxide was added thereto as a polymerization catalyst in an amount of 250 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
  • a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerisation to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
  • a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A and 5% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
  • a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 3.
  • a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid and 150 parts by mole of ethylene glycol.
  • Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
  • a heat shrinkable polyester film having a thickness of 40 ⁇ m was prepared from the resultant polyester resin in the same manner as that of Example 1.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
  • a reaction vessel was charged with 93 parts by mole of terephthalic acid, 7 parts by mole of isophthalic acid and 140 parts by mole of ethylene glycol. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
  • a reaction vessel was charged with 100 parts by mole of terephthalic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
  • a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of sebacic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A.
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to give a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
  • a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film and provided in Table 3.
  • the heat shrinkable polyester films of Examples 10 to 14 according to the present invention exhibited a shrinkage initiation temperature of 50°C or below and a percentage heat shrinkage of 20% or more at 60°C, and substantially no uneven shrinkage was observed.
  • isophthalic-acid-based polyester films of Comparative Examples 9 and 10 exhibited a large shrinkage at a high temperature, shrinking properties at a low temperature were poor and, at the same time, the occurrence of uneven shrinkage was observed, so that these films were not practical.
  • polyester films containing an ethylene oxide adduct of bisphenol A of Comparative Examples 11 to 13 although the occurrence of uneven shrinkage was slightly alleviated as compared with Comparative Examples 9 and 10, the alleviation is not yet satisfactory and the shrinking properties at a low temperature as well were poor.
  • a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
  • a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
  • a reaction vessel was charged with 80 parts by mole of terephthalic acid, 15 parts by mole of isophthalic acid, 5 parts by mole of sebacic acid and 150 parts by mole of ethylene glycol.
  • Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
  • a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of sebacic acid, 150 parts by mole of ethylene glycol and 20 parts by mole of neopentyl glycol.
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component
  • antimony trioxide and zinc acetate were added thereto as a polymerization catalyst in respective amounts of 450 ppm and 100 ppm each based on the whole acid component.
  • Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
  • a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
  • a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
  • a reaction vessel was charged with 75 parts by mole of terephthalic acid, 25 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
  • Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
  • antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
  • Polymerization was conducted by direct polymerization to provide a polyester resin.
  • the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
  • the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
  • the results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
  • the heat shrinkable polyester films of Examples 16 to 18 were free from the occurrence of uneven shrinkage and, at the same time, excellent in the solvent bondability.
  • the heat shrinkable polyester film of Example 12 wherein the amount of copolymerization of isophthalic acid, although no uneven shrinkage was observed, the solvent bondability was relatively poor.
  • the heat shrinkable polyester films of Comparative Examples 9 and 10 were unsatisfactory both in the occurrence of uneven shrinkage and solvent bondability.

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Claims (19)

  1. Film de polyester thermorétractable comprenant une résine polyester comprenant des unités d'un constituant d'acide dicarboxylique principalement constitué d'un acide dicarboxylique aromatique et d'un constituant de diol principalement constitué d'éthylèneglycol et d'un produit d'addition d'un composé bisphénol avec de l'oxyde d'éthylène, la teneur d'un produit d'addition d'un composé bisphénol avec de l'oxyde d'éthylène étant de 0,5 à 30% en mole, rapportés au constituant total de diol, ladite résine comprenant en outre de 0,1 à 20% en poids d'unités de polyoxytétraméthylèneglycol et/ou de polyéthyléneglycol.
  2. Film de polyester thermorétractable selon la revendication 1, dans lequel la teneur des unités de polyoxytétraméthylèneglycol et/ou de polyéthylèneglycol est de 0,3 15% en poids.
  3. Film de polyester thermorétractable selon la revendication 1, dans lequel le polyoxytétraméthylèneglycol a un poids moléculaire de 300 à 4 000.
  4. Film de polyester thermorétractable selon la revendication 1, dans lequel le polyéthylèneglycol a un poids moléculaire de 300 à 20 000.
  5. Film de polyester thermorétractable selon la revendication 1, qui comprend en outre de 0,01 à 1% en poids d'unités d'un acide tricarboxylique ou polycarboxylique supérieur et/ou d'un alcool trivalent ou polyvalent supérieur.
  6. Film de polyester thermorétractable selon la revendication 1, qui comprend en outre de 0,05 à 0,7% en poids d'unités d'un acide tricarboxylique ou polycarboxylique supérieur et/ou d'un alcool trivalent ou polyvalent supérieur.
  7. Film de polyester thermorétractable selon la revendication 1, dans lequel l'acide polycarboxylique est choisi parmi l'acide trimellitique, l'acide pyromellitique et leurs anhydrides.
  8. Film de polyester thermorétractable selon la revendication 1, dans lequel l'alcool polyvalent est choisi parmi le triméthylolpropane, la glycérine et le pentaérythritol.
  9. Film de polyester thermorétractable selon la revendication 1, dans lequel le produit d'addition d'un composé de bisphénol avec de l'oxyde d'éthylène est un produit d'addition de bisphénol A avec de l'oxyde d'éthylène.
  10. Film de polyester thermorétractable selon la revendication 1, dans lequel le produit d'addition d'un composé de bisphénol avec de l'oxyde d'éthylène est un produit d'addition de bisphénol S avec de l'oxyde d'éthylène.
  11. Film de polyester thermorétractable selon la revendication 1, dans lequel le constituant d'acide dicarboxylique est principalement constitué d'acide téréphtalique et d'acide isophtalique et l'acide isophtalique est contenu dans une quantité de 7 à 30% en mole, rapportés au constituant d'acide dicarboxylique total.
  12. Film de polyester thermorétractable selon la revendication 11, dans lequel l'acide isophtalique est contenu dans une quantité de 10 à 30% en mole, rapportés au constituant d'acide dicarboxylique total.
  13. Film de polyester thermorétractable selon la revendication 11, dans lequel l'acide isophtalique est contenu dans une quantité de 12 à 30% en mole, rapportés au constituant d'acide dicarboxylique total.
  14. Film de polyester thermorétractable selon la revendication 1, qui présente un pourcentage de retrait de 20% ou supérieur à 60°C dans une seule direction lorsque le film est chauffé dans un bain d'eau chaude pendant 60 s.
  15. Film de polyester thermorétractable selon la revendication 14, qui présente un pourcentage de retrait de 25% ou supérieur à 60°C dans une seule direction lorsque le film est chauffé dans un bain d'eau chaude pendant 60 s.
  16. Film de polyester thermorétractable selon la revendication 14, qui présente un pourcentage de retrait de 30% ou supérieur à 60°C dans une seule direction lorsque le film est chauffé dans un bain d'eau chaude pendant 60 s.
  17. Film de polyester thermorétractable selon la revendication 14, qui présente un pourcentage de retrait de 1% ou supérieur à 50°C dans une seule direction lorsque le film est chauffé dans un bain d'eau chaude pendant 60 s.
  18. Film de polyester thermorétractable selon la revendication 14, qui présente un pourcentage de retrait de 2% ou supérieur à 50°C dans une seule direction lorsque le film est chauffé dans un bain d'eau chaude pendant 60 s.
  19. Film de polyester thermorétractable selon la revendication 1, qui présente une vitesse de retrait moyenne dans l'intervalle de 0,3 à 3%/s sur une durée entre 0 s et 10 s, entre 10 s et 20 s et entre 20 s et 30 s après l'initiation de l'immersion dudit film dans un bain d'eau chaude.
EP19920114522 1991-08-28 1992-08-26 Résine de polyester et son utilisation Expired - Lifetime EP0532943B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96110825A EP0741166A3 (fr) 1991-08-28 1992-08-26 Bouteille en polyester moulée directement
EP96110824A EP0741161A3 (fr) 1991-08-28 1992-08-26 Feuille en polyester thermorétractable

Applications Claiming Priority (20)

Application Number Priority Date Filing Date Title
JP21723291 1991-08-28
JP217232/91 1991-08-28
JP217231/91 1991-08-28
JP21723191 1991-08-28
JP4907/92 1992-01-14
JP490792A JPH05186579A (ja) 1992-01-14 1992-01-14 ダイレクトブロー用ポリエステル樹脂
JP52904/92 1992-03-11
JP5290492A JPH0565338A (ja) 1991-07-11 1992-03-11 変性ポリエステル樹脂
JP110964/92 1992-04-30
JP11096792 1992-04-30
JP11096392A JPH05305663A (ja) 1992-04-30 1992-04-30 熱収縮性ポリエステルフィルム
JP110965/92 1992-04-30
JP11096492A JPH05305664A (ja) 1992-04-30 1992-04-30 熱収縮性ポリエステルフィルム
JP11096592A JPH05261816A (ja) 1991-08-28 1992-04-30 熱収縮性ポリエステルフィルム
JP110967/92 1992-04-30
JP110963/92 1992-04-30
JP110966/92 1992-04-30
JP11096692 1992-04-30
JP4114890A JPH068322A (ja) 1991-08-28 1992-05-07 熱収縮性ポリエステルフィルム
JP114890/92 1992-05-07

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP96110824A Division EP0741161A3 (fr) 1991-08-28 1992-08-26 Feuille en polyester thermorétractable
EP96110825A Division EP0741166A3 (fr) 1991-08-28 1992-08-26 Bouteille en polyester moulée directement

Publications (2)

Publication Number Publication Date
EP0532943A1 EP0532943A1 (fr) 1993-03-24
EP0532943B1 true EP0532943B1 (fr) 1998-06-10

Family

ID=27579527

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920114522 Expired - Lifetime EP0532943B1 (fr) 1991-08-28 1992-08-26 Résine de polyester et son utilisation

Country Status (2)

Country Link
EP (1) EP0532943B1 (fr)
DE (1) DE69225855T2 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0561596B2 (fr) * 1992-03-19 2001-12-19 Teijin Limited Film orienté de polyester
US5932685A (en) * 1996-08-30 1999-08-03 Toyo Boseki Kabushiki Kaisha Heat-shrinkable polyester films
JP3642229B2 (ja) 1999-05-21 2005-04-27 東洋紡績株式会社 熱収縮性ポリエステル系フィルム
TW583264B (en) * 2001-09-26 2004-04-11 Nanya Plastics Corp Improved copolyester with improved extrusion processing and color for extrusion blow molding
DE10354732A1 (de) * 2003-11-21 2005-06-16 Zimmer Ag Verfahren zur Herstellung von PET-Folien
CN115613365A (zh) * 2022-11-14 2023-01-17 江苏动亦智能自动化科技有限公司 一种高温带无缝环的加工工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2402841A1 (de) * 1974-01-22 1975-07-24 Mehnert & Veeck Kg Lackfabrik Loesungsmittelarme, niedrigviskose polyester
JPS5277294A (en) * 1975-12-23 1977-06-29 Kao Corp Glass fiber bundling agent
EP0271928B1 (fr) * 1986-12-19 1997-04-16 Toyo Boseki Kabushiki Kaisha Feuille en polyester thermorétrécissable
DE68926993T2 (de) * 1988-12-01 2003-05-28 Mitsubishi Rayon Co Toner
JPH0733064B2 (ja) * 1988-12-07 1995-04-12 ダイアホイルヘキスト株式会社 ポリエステル系収縮フィルム

Also Published As

Publication number Publication date
EP0532943A1 (fr) 1993-03-24
DE69225855T2 (de) 1998-11-12
DE69225855D1 (de) 1998-07-16

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